US3401184A - Metal organo phosphate preparation process - Google Patents
Metal organo phosphate preparation process Download PDFInfo
- Publication number
- US3401184A US3401184A US350113A US35011364A US3401184A US 3401184 A US3401184 A US 3401184A US 350113 A US350113 A US 350113A US 35011364 A US35011364 A US 35011364A US 3401184 A US3401184 A US 3401184A
- Authority
- US
- United States
- Prior art keywords
- orthophosphate
- metal
- bis
- ethylhexyl
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229910052751 metal Inorganic materials 0.000 title description 53
- 239000002184 metal Substances 0.000 title description 53
- -1 organo phosphate Chemical compound 0.000 title description 47
- 238000002360 preparation method Methods 0.000 title description 5
- 229910019142 PO4 Inorganic materials 0.000 title description 3
- 239000010452 phosphate Substances 0.000 title description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 55
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 47
- 150000002430 hydrocarbons Chemical group 0.000 description 29
- 238000006243 chemical reaction Methods 0.000 description 28
- 229930195733 hydrocarbon Natural products 0.000 description 25
- 229910001507 metal halide Inorganic materials 0.000 description 24
- 150000005309 metal halides Chemical class 0.000 description 24
- 239000004215 Carbon black (E152) Substances 0.000 description 22
- 239000000203 mixture Substances 0.000 description 21
- 238000000034 method Methods 0.000 description 19
- LJKDOMVGKKPJBH-UHFFFAOYSA-N 2-ethylhexyl dihydrogen phosphate Chemical compound CCCCC(CC)COP(O)(O)=O LJKDOMVGKKPJBH-UHFFFAOYSA-N 0.000 description 18
- 125000000962 organic group Chemical group 0.000 description 18
- 125000004432 carbon atom Chemical group C* 0.000 description 15
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 13
- 239000000376 reactant Substances 0.000 description 13
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 12
- 239000003960 organic solvent Substances 0.000 description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 150000002367 halogens Chemical group 0.000 description 9
- 239000010936 titanium Substances 0.000 description 9
- 229910052719 titanium Inorganic materials 0.000 description 9
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 8
- 125000001183 hydrocarbyl group Chemical group 0.000 description 8
- 229910000039 hydrogen halide Inorganic materials 0.000 description 8
- 239000012433 hydrogen halide Substances 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 229910052736 halogen Inorganic materials 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 5
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 5
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 5
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical compound [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- XDFCIPNJCBUZJN-UHFFFAOYSA-N barium(2+) Chemical compound [Ba+2] XDFCIPNJCBUZJN-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052811 halogen oxide Inorganic materials 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 125000001117 oleyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 230000000737 periodic effect Effects 0.000 description 3
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 3
- NMRPBPVERJPACX-UHFFFAOYSA-N (3S)-octan-3-ol Natural products CCCCCC(O)CC NMRPBPVERJPACX-UHFFFAOYSA-N 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- WOFPPJOZXUTRAU-UHFFFAOYSA-N 2-Ethyl-1-hexanol Natural products CCCCC(O)CCC WOFPPJOZXUTRAU-UHFFFAOYSA-N 0.000 description 2
- YQUQWHNMBPIWGK-UHFFFAOYSA-N 4-isopropylphenol Chemical compound CC(C)C1=CC=C(O)C=C1 YQUQWHNMBPIWGK-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- 235000019445 benzyl alcohol Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 125000000853 cresyl group Chemical group C1(=CC=C(C=C1)C)* 0.000 description 2
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- MKANCOHERYHKAT-UHFFFAOYSA-L dibenzyltin(2+);dichloride Chemical compound C=1C=CC=CC=1C[Sn](Cl)(Cl)CC1=CC=CC=C1 MKANCOHERYHKAT-UHFFFAOYSA-L 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000004820 halides Chemical group 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 229960004592 isopropanol Drugs 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 235000011150 stannous chloride Nutrition 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- CMWCOKOTCLFJOP-UHFFFAOYSA-N titanium(3+) Chemical compound [Ti+3] CMWCOKOTCLFJOP-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
- JXNPEDYJTDQORS-HZJYTTRNSA-N (9Z,12Z)-octadecadien-1-ol Chemical compound CCCCC\C=C/C\C=C/CCCCCCCCO JXNPEDYJTDQORS-HZJYTTRNSA-N 0.000 description 1
- GJYMQFMQRRNLCY-ONEGZZNKSA-N (e)-pent-3-en-2-ol Chemical compound C\C=C\C(C)O GJYMQFMQRRNLCY-ONEGZZNKSA-N 0.000 description 1
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 1
- VUZPGEIXNYGDJN-UHFFFAOYSA-N 1-nitroethanol Chemical compound CC(O)[N+]([O-])=O VUZPGEIXNYGDJN-UHFFFAOYSA-N 0.000 description 1
- CWPPDTVYIJETDF-UHFFFAOYSA-N 2,2,4-trimethylpentan-1-ol Chemical compound CC(C)CC(C)(C)CO CWPPDTVYIJETDF-UHFFFAOYSA-N 0.000 description 1
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical compound CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 description 1
- QTJURDURBMIUFX-UHFFFAOYSA-N 3-ethylnonan-1-ol Chemical compound CCCCCCC(CC)CCO QTJURDURBMIUFX-UHFFFAOYSA-N 0.000 description 1
- WMLDVNFSAVPBBH-UHFFFAOYSA-N 3-propan-2-ylcyclohexan-1-ol Chemical compound CC(C)C1CCCC(O)C1 WMLDVNFSAVPBBH-UHFFFAOYSA-N 0.000 description 1
- UZFMOKQJFYMBGY-UHFFFAOYSA-N 4-hydroxy-TEMPO Chemical compound CC1(C)CC(O)CC(C)(C)N1[O] UZFMOKQJFYMBGY-UHFFFAOYSA-N 0.000 description 1
- NTDQQZYCCIDJRK-UHFFFAOYSA-N 4-octylphenol Chemical compound CCCCCCCCC1=CC=C(O)C=C1 NTDQQZYCCIDJRK-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910021581 Cobalt(III) chloride Inorganic materials 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910021585 Nickel(II) bromide Inorganic materials 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910001622 calcium bromide Inorganic materials 0.000 description 1
- WGEFECGEFUFIQW-UHFFFAOYSA-L calcium dibromide Chemical compound [Ca+2].[Br-].[Br-] WGEFECGEFUFIQW-UHFFFAOYSA-L 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229960000359 chromic chloride Drugs 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- LJAOOBNHPFKCDR-UHFFFAOYSA-K chromium(3+) trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[Cr+3] LJAOOBNHPFKCDR-UHFFFAOYSA-K 0.000 description 1
- 239000011636 chromium(III) chloride Substances 0.000 description 1
- 235000007831 chromium(III) chloride Nutrition 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 229940097267 cobaltous chloride Drugs 0.000 description 1
- 229940125810 compound 20 Drugs 0.000 description 1
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- VUNFOJWKJSYIDH-UHFFFAOYSA-N dec-4-en-1-ol Chemical compound CCCCCC=CCCCO VUNFOJWKJSYIDH-UHFFFAOYSA-N 0.000 description 1
- VKHDSOXSTURPAJ-UHFFFAOYSA-L dibenzyl(dibromo)stannane Chemical compound C=1C=CC=CC=1C[Sn](Br)(Br)CC1=CC=CC=C1 VKHDSOXSTURPAJ-UHFFFAOYSA-L 0.000 description 1
- SVSRQMUJHHQAAX-UHFFFAOYSA-N dibenzyltin Chemical group C=1C=CC=CC=1C[Sn]CC1=CC=CC=C1 SVSRQMUJHHQAAX-UHFFFAOYSA-N 0.000 description 1
- QSGGLKRQVLBHKX-UHFFFAOYSA-L dibromo(diethyl)stannane Chemical compound CC[Sn](Br)(Br)CC QSGGLKRQVLBHKX-UHFFFAOYSA-L 0.000 description 1
- ALOQGPVOAWHHLG-UHFFFAOYSA-L diphenyltin(2+);dibromide Chemical compound C=1C=CC=CC=1[Sn](Br)(Br)C1=CC=CC=C1 ALOQGPVOAWHHLG-UHFFFAOYSA-L 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical class CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- FLXZKIIRMUPJOE-UHFFFAOYSA-L ethyl(propyl)tin(2+);dichloride Chemical compound CCC[Sn](Cl)(Cl)CC FLXZKIIRMUPJOE-UHFFFAOYSA-L 0.000 description 1
- CYRHQOOURDSWBR-UHFFFAOYSA-K ethyl(triiodo)stannane Chemical compound CC[Sn](I)(I)I CYRHQOOURDSWBR-UHFFFAOYSA-K 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- CULSIAXQVSZNSV-UHFFFAOYSA-N germanium(4+) Chemical compound [Ge+4] CULSIAXQVSZNSV-UHFFFAOYSA-N 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- LRGKLCMGBJZMTB-UHFFFAOYSA-J hydrogen phosphate;tin(4+) Chemical group [Sn+4].OP([O-])([O-])=O.OP([O-])([O-])=O LRGKLCMGBJZMTB-UHFFFAOYSA-J 0.000 description 1
- 150000002440 hydroxy compounds Chemical class 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 description 1
- JXNPEDYJTDQORS-UHFFFAOYSA-N linoleyl alcohol Natural products CCCCCC=CCC=CCCCCCCCCO JXNPEDYJTDQORS-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000003340 mental effect Effects 0.000 description 1
- 229960002523 mercuric chloride Drugs 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- LWJROJCJINYWOX-UHFFFAOYSA-L mercury dichloride Chemical compound Cl[Hg]Cl LWJROJCJINYWOX-UHFFFAOYSA-L 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 239000010688 mineral lubricating oil Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- OYMJNIHGVDEDFX-UHFFFAOYSA-J molybdenum tetrachloride Chemical compound Cl[Mo](Cl)(Cl)Cl OYMJNIHGVDEDFX-UHFFFAOYSA-J 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229940078552 o-xylene Drugs 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229940055577 oleyl alcohol Drugs 0.000 description 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- IEXRMSFAVATTJX-UHFFFAOYSA-N tetrachlorogermane Chemical compound Cl[Ge](Cl)(Cl)Cl IEXRMSFAVATTJX-UHFFFAOYSA-N 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 description 1
- NLLZTRMHNHVXJJ-UHFFFAOYSA-J titanium tetraiodide Chemical compound I[Ti](I)(I)I NLLZTRMHNHVXJJ-UHFFFAOYSA-J 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- CURXGOYGFWMBRW-UHFFFAOYSA-N zirconium(3+) Chemical compound [Zr+3] CURXGOYGFWMBRW-UHFFFAOYSA-N 0.000 description 1
- LSWWNKUULMMMIL-UHFFFAOYSA-J zirconium(iv) bromide Chemical compound Br[Zr](Br)(Br)Br LSWWNKUULMMMIL-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/26—Organic compounds containing phosphorus
- C10L1/2633—Organic compounds containing phosphorus phosphorus bond to oxygen (no P. C. bond)
- C10L1/2641—Organic compounds containing phosphorus phosphorus bond to oxygen (no P. C. bond) oxygen bonds only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/26—Organic compounds containing phosphorus
- C10L1/2633—Organic compounds containing phosphorus phosphorus bond to oxygen (no P. C. bond)
- C10L1/2658—Organic compounds containing phosphorus phosphorus bond to oxygen (no P. C. bond) amine salts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/30—Organic compounds compounds not mentioned before (complexes)
- C10L1/301—Organic compounds compounds not mentioned before (complexes) derived from metals
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/108—Residual fractions, e.g. bright stocks
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/043—Ammonium or amine salts thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/02—Groups 1 or 11
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/04—Groups 2 or 12
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/08—Groups 4 or 14
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/12—Groups 6 or 16
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/14—Group 7
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/16—Groups 8, 9, or 10
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
Definitions
- R is a A process for preparing metal organo orthophosphates hydrocarbon group having from 1 to about 30 carbon by contacting at a temperature from about 10 C. to about atoms
- X is a halogen
- M is a polyvalent metal:
- M is valent metal halide in an inert organic solvent with an divalent in Equation I; M is tetravalent in Equation II; organic hydroxyl having from 1 to about carbon atoms. whereas M is trivalent in Equation III.
- metal organo orthophosphates of generic chloride are dispersed in the organic solvent and reacted Equation I are referred to as metal (II) [di(hydrocarbyl) at a temperature between 10 C. and 60 C. with added 30 orthophosphate] [monoacid mono(hydrocarbyl) orthoethylhexanol. Subsequent raising of the temperature to phosphate]; those of generic Equation II are referred to as between 80 C., and 110 C.
- the polyvalent metal halide employed in this in- This invention relates to the preparation of metal vention can be represented by the formula: organo orthophosphates. More particularly it relates to the preparation of such orthophosphates by reacting an R nMXn organic hydroxyl compound with a polyvalent metal halide and phosphorus pentcxide.
- Metal organo orthophosphates can be prepared by reacting an organic acid orthophosphate with a polyvalent metal halide.
- the commercially available organic acid orthophosphates are generally mixtures of the monoand diacid orthophosphates in various proportions and free phosphoric acid is often present as an impurity.
- a metal organo orthophosphate of reproducible composition is difiicult to obtain from the commercially available organic acid orthophosphate reactants. Also, it is often necessary to remove the free phosphoric acid impurity prior to reaction with the polyvalent metal halide.
- metal organo orthophosphates can be prepared by reacting an organic hydroxyl containing compound with a polyvalent metal halide and phosphorus pentoxide in an inert organic solvent.
- the reaction is conducted by simply admixing the reactants at a temperature of from about 10 C. to about 120 C.
- the halide groups of the metal are displaced to form a salt of the metal with at least two orthophosphate groups
- (n) is an integer of 0 to 2
- M is a polyvalent metal
- X is a halogen
- (n) is an integer of at least 2, such as 2 to 4 or 6 and the total of (n) and (ri') is equal to the valence of the metal M.
- the polyvalent metal halide is one represented by the formula MX wherein M is a polyvalent metal having a valence of 2-4, X is a halogen and n is an integer equal to the valence of the metal, i.e. 24.
- the metal can be one from Group II, Group IV, Group VI and Group VIII of Mandeleeffs Periodic Arrangements of the Elements. A copy of this arrangement, referred to herein as the Periodic Arrangement, can be found on pages 3l2313 of the Handbook of Chemistry and Physics, 29th edition (1945).
- the preferred metals employed in this invention are the tetravalent metals of Group IV which have an automatic number of 22 to 40 such as titanium and zirconium.
- the halogen can be fluorine, chlorine, bromine or iodine and preferably chlorine.
- magnesium chloride magnesium fluoride; calcium bromide, zine bromide; zinc chloride; barium co ple s 0 6 Or more Ester g p 011 each f the OfthO- chloride; mercuric chloride; stannous chloride; stannic phosphate groups attached to the metal.
- lead chloride titanium trichloride; titanium tetraester formation and linkage to the metal, one or more of chloride; titanium tetrafiuoride; titanium tetrabromide;
- R is a hydrocarbon group having from 1 to about.
- titanium tetraiodide germanium tetrachloride; molybdenum tetrachloride; chromic chloride; zirconium tetrachloride; zirconium tetrabromide; cobaltic chloride; cobaltous chloride; nickel bromide; nickel chloride; dibenzyl tin dibromide; dibenzyl tin dichloride; diethyl tin dibromide; disioamyl tin dichloride; diphenyl tin dibromide; ethyl propyl tin dichloride; ethyl tin triiodide; and the like.
- the organic hydroxyl compound can have from 1 to about 30 carbon atoms.
- the organic hydroxyl compound is a monohydroxy hydrocarbon which can be represented by the formula ROH wherein R is a hydrocarbon group having from 1 to 30 carbon atoms and preferably from about 6 to about 22 carbon atoms.
- the hydroxyl group can be linked to an aliphatic, cycloaliphatic or aromatic hydrocarbon group.
- the monohydroxy, hydrocarbon can thus be alkanol, alkenol, cycloalkanol, cycloalkenol, phenol, phenalkanol, alkphenol and the like.
- the monohydroxy hydrocarbon is alkanol and particularly branched chain alkanol. Illustrative of specific monohydroxy hydrocarbon reactants there can be mentioned: methanol; ethanol; propanol; isopr-opanol; bu-
- dipropyldodecanol 2,2,3-trirnethylheptanol; 3-ethylnonanol; 2-methyl-5-isopentylhendecanol; dodecanol; 6,7-dipentyldodecanol; 9,12-dimethyleicosanol; oleyl alcohol; linoleyl alcohol; 3-pentene-2-ol; cyclohexanol; 3-isopropylcyclohexanol; 4-decen-l-ol; 4-octylphenol; 4-isopropylphenol; 4 phenyl l-hydroxydodecane; phenol; alphanaphthol; benzyl alcohol; and the like.
- either one or a mixture of organic hydroxyl compounds can be employed.
- the hydrocarbon portion of the hydroxyl containing organic compound can be substituted with various groups which do not interfere with the reaction.
- substituent groups on the hydrocarbon group there can be mentioned nitro groups, such as in nitroalkanols, e.g. nitroethanol, and ammonium groups such as in ammonium alkenols, e.g. the lauric acid salt of ethanolamine.
- the temperature employed in the process of this invention can vary over a wide range such as that of from about C. to about 120 C., preferably from about C. to about 110 C. and particularly from about C. to about 105 C.
- the molar ratio of the reactants employed in the process of this invention can vary over a wide range such as that of from about 0.1 to 5 moles of phosphorus pentoxide and from about 1 to about 10 moles of the organic hydroxyl compound per mole of the metal halide and P eferably from about 0.5 to 3 moles of phosphorus pentoxide and 2 to 8 moles of the organic hydroxy compound per mole of the metal halide.
- the optimum molar ratio will, of course, vary with the particular reactants and particularly with the number of halogens attached to the metal, as can be seen from the hereinabove generic Equations I-III.
- the organic hydroxyl compound be added to a mixture of the metal halide and phosphorus pentoxide in an inert organic solvent at a temperature not higher than about 60 C. such as that of from about 10 C. to about 60 C.
- Addition of the organic hydroxyl compound to a mixture of phosphorus pentoxide and the metal halide is preferred since it minimizes reaction of the metal halide directly with the organic hydroxyl compound. Reaction of the metal halide and organic hydroxyl compound eliminates available reaction sites on the metal for the phosphate due to formation of a metal salt of the hydroxyl reactant.
- the initial contact of the hydroxyl reactant with the mixture of phosphorus pentoxide and metal halide is preferably at a temperature no higher, or below, 60 C. to prevent unduly rapid reaction rates.
- the reaction is preferably completed by raising the reaction temperature, e.g. from about 80 C. to the maximum temperatures of the reaction hcreinbefore set forth, such as about 110 C. Also, it is desirable to provide means for removing the hydrogen halide formed in the reaction.
- a stoichiometric excess of the hydroxyl reactant can be employed in order to improve the yield of desired end product.
- a large excess such as that of more than 1.5 or twice the calculated molar ratio of hydroxyl compound for the particular reaction is preferably avoided since it may be desirable to later separate the excess hydroxyl compound from the reaction mixture in order to recover the desired reaction product.
- reaction time in the process of this invention is not critical. Thus it can vary from less than about half an hour to two or three days and preferably from about 2 or 3 hours to a day or two.
- the metal organo orthophosphates can be recovered from the reaction mixture by conventional techniques such as fractional distillation, chromatographic absorption and the like. However, it is possible, although not generally desirable, to use the products without separation from the reaction mixture as additives to hydrocarbon fuels or mineral lubricating oils.
- Suitable inert organic solvents for the process of this invention include various classes of compounds such as hydrocarbons, halogenated hydrocarbons and others.
- inert it is mean that the solvent is inert to the reactants and reaction products under the reaction conditions.
- Suitable solvents include benzene, toluene, uxylene, o-xylene, m-xylene, hexane, heptane, octane, cyclohexane, methylcyclohexane, chlorobenzene, carbon tetrachloride, ethyl ether, tetrahydrofurane, and the like.
- Preferred organic solvents are the normally liquid hydrocarbons such as the various aromatic, aliphatic and cycloaliphatic hydrocarbons.
- the equipment used in the reaction should be immune to attack by gaseous hydrogen halide.
- the reaction vessel should be equipped with a heater, a mechanical stirrer, a pressure equalizing addition vessel, a reaction temperature indicator, and an inlet for compressed dry air to displace by-product hydrogen halide through a reflux condenser that does not permit entry of moisture from the outside. It is highly desirable to maintain a water-free atmosphere in the reactor.
- Two moles of phosphorus pentoxide is dispersed uniformly by means of mechanical agitation in a hydrocarbon solvent such as anhydrous n-heptane in the reaction vessel.
- One mole of tetravalent metal halide is added next with enough stirring to prevent agglomeration of the materials.
- the metal organo orthophosphates prepared by the process of this invention have utility as additives in bydrocarbon fuel compositions, e.g. gasoline.
- bydrocarbon fuel compositions e.g. gasoline.
- small quantities of the metal organo orthophosphates e.g. 100 parts per million based on the weight of the gasoline composition, impart rust inhibition, surface ignition suppression, carburetor detergency, carburetor icing alleviation, and reduction in octane requirement increase to the gasoline composition.
- the metal organo orthophosphates have utility as anti-wear agents in mineral oil lubricants wherein they can be employed in concentrations of about 1% by Weight of the composition.
- the metal organo orthophosphates which have a free acid group e.g. those of the hereinabove described generic Equations I and II, be neutralized with an organic amine prior to their use as hydrocarbon additives.
- the free acid groups can be neutralized at about 30 C. by contact with oleyl amine.
- metal organo orthophosphates which can be prepared in accordance with the hereinbefore described generic Equation II, there can be mentioned: titanium (IV) bis[di(Z-ethylhexyl) orthophosphate] bis[monoacid mono (2-ethylhexyl) orthophosphate] titanium (IV) bis[di(4-octylphenyl) orthophosphate] bis[monoacid mono(4-octylphenyl) orthophosphate]; titanium (IV) bis[di(ethyl) orthophosphate] bis[monoacid mono(ethyl) orthophosphate]; titanium (IV) [di(ndodecyl) orthophosphate] bis[monoacid mono(n-dodecyl) orthophosphate]; titanium (IV) bis[di(oleyl) orthophosphate] bis[monoacid dioleyl orthophosphate]; titanium (IV) bis[dibenzyl orthophosphate] bis[[di(
- Titanium (IV) bis[di(Z-ethylhexyl) orthophosphate] bis[mono(2-ethylhexyl) monoacid orthophosphate] is obtained from the reaction of 2 moles of phosphorous pentoxide and one mole of titanium tetrachloride with 6 moles of 2-ethyl-1-hexanol as shown below:
- Example 2 In the manner described in Example 1 a mixture of two moles (284 g.) of P 0 and one mole (233 g.) of zirconium tetrachloride in anhydrous n-heptane is reacted with a blend of 3.1 moles (96 g.) of methanol and 3.1 moles (404 g.) of 2-ethylhexanol to produce zirconium (IV) bis[mono (methyl) mono(2ethylhexyl) orthophosphate] [monoacid mono (2-ethylhexyl) orthophosphate] [monoacid mono(methyl) orthophosphate] EXAMPLE 3 In the manner described in Example 1,142 g.
- a process for preparing a metal organo orthophosphate which comprises: (a) contacting, in an inert organic solvent, phosphorus pentoxide; and (b) a polyvalent metal halide of the formula MX wherein M is a polyvalent metal, selected from the group consisting of magnesium, calcium, zinc, barium, mercury, lead, titanium, germanium, molybdenum, chromium, zirconium, cobalt, nickel and tin, X is a halogen and .n is equal to the valence of the metal M; with (c) a monohydroxy hydrocarbon having from 1 to about carbon atoms at a tempera ture of from about 10 C, to about 120 C.
- a process of claim 1 wherein the monohydroxy hydrocarbon is alkanol having from about 6 to about 22 carbon atoms and is added at a rate to produce a steady evolution of gaseous hydrogen halide.
- a process for preparing a metal organo orthophosphate which comprises: (a) contacting, at a temperature 3 of from about 20 C. to about C., a monohydroxy hydrocarbon having from 1 to about 30 carbon atoms; with (b) a mixture of titanium tetrachloride and phosphorus pentoxide in an inert organic solvent.
- a process for preparing a metal organo orthophosphate which comprises: (a) contacting, at a temperature of from about 20 C. to about 110 (3., a monohydroxy hydrocarbon having from 1 to about 30 carbon atoms; with (b) a mixture of zirconium tetrachloride and phosphorus pentoxide in an inert organic solvent,
- M is a tetravalent metal
- each R is hydrocarbyl of from 1 to about 30 carbon atoms, which comprises: (a) reacting at a temperature of from about 20 C. to about 110 C., a monohydroxy hydrocarbon having from 1 to about 30 carbon atoms; with (b) a mixture of tetravalent metal halide of the formula MX wherein M is tetravalent metal and X is halogen and phosphorus pentoxide in an inert organic solvent.
- M is a metal having an atomic number of 22 to 40 from Group IV of the Periodic Arrangement and about 2 moles of phosphorus pentoxide and about 6 moles of the monohydroxy hydrocarbon are reacted with each mole of the tetravalent halide.
- each R is hydrocarbyl of from 1 to about 30 carbon atoms and M is a divalent metal which comprises: (a) contacting at a temperature of from about 20 C. to about 110 C. a monohydroxy hydrocarbon having from 1 to about 30 carbon atoms; with a mixture of a divalent metal halide of the formula MX wherein M is a metal and X is halogen and phosphorus pentoxide in an inert organic solvent.
- R is hydrocarbyl of from 1 to about 30 carbon atoms and M is a trivalent metal which comprises: (a) contacting, at a temperature of from about 20 C. to about 110 C. a monohydric hydrocarbon having from 1 to about 30 carbon atoms; (b) with a mixture of a metal halide of the formula MX wherein M is a trivalent metal and X is halogen and phosphorus pentoxide in an inert organic solvent.
- a process for preparing titanium (IV) -bis[di(2- ethylhexyl) orthorphosphate] .bis[n1onoacid mono(2- ethylhexyl) orthophosphate] which comprises: (a) dispersing phosphorus pentoxide and titanium tetrachloride in an inert hydrocarbon solvent; (b) adding and reacting References Cited UNITED STATES PATENTS 2,272,668 2/1942 Honel 260933X 10 Farrington et a1. 2604297 X Mack et a1. 260439X Fortress et a1. 260980 Otto et a1. 260933X Giammaria 260933 X Heyden 2'60429.5 X Wurstner 260429.7X Revukas 260--429.5 X
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Description
3,401,184 Patented Sept. 10, 1968 l nited States Patent l 3 401 184 the phosphate groups can contain an acid group. Hydrogen halide is a by-product of the reaction.
Preparation of the metal organo orthophosphates di- Anthony J. Revukas, Cranford, N..I., assignor to Citi rectly from the raw materials avoids the need of an Service Oil Company, a corporation of Delaware 5 organic acid orthophosphate intermediate; it reduces the No Drawing. Filed Mar. 6, 1964, Ser. No. 350,113
amount of process effort, and affords a process for the Claims. (Cl. 260-429.3)
preparation of a large variety of metal organo orthophosphates.
The below listed generic equations show typical re- ABSTRACT 0F THE DISCLOSURE 10 actions of the process of this invention wherein R is a A process for preparing metal organo orthophosphates hydrocarbon group having from 1 to about 30 carbon by contacting at a temperature from about 10 C. to about atoms X is a halogen, and M is a polyvalent metal:
r P205 3ROH MXz (RO)2POMOP/ 2HX I OH i 57 21205 GROH MX4 [(RO-)2PO]2M -O-P 4HX .11
o 0 ll \ll P205 3.11011 MX3 (BO-) P-O-M P-OR 3HX III 0 120 C., a mixture of phosphorus pentoxide and a poly- 25 It can be seen that in the above generic equations: M is valent metal halide in an inert organic solvent with an divalent in Equation I; M is tetravalent in Equation II; organic hydroxyl having from 1 to about carbon atoms. whereas M is trivalent in Equation III. In the above generic Preferably the phosphorus pentoxide and titanium tetraequations: metal organo orthophosphates of generic chloride are dispersed in the organic solvent and reacted Equation I are referred to as metal (II) [di(hydrocarbyl) at a temperature between 10 C. and 60 C. with added 30 orthophosphate] [monoacid mono(hydrocarbyl) orthoethylhexanol. Subsequent raising of the temperature to phosphate]; those of generic Equation II are referred to as between 80 C., and 110 C. results in evolution of the a metal (IV) bis [di (hydrocarbyl) orthosphosphate] bis HCl formed yielding as residue titanium (IV) his [di 2- [monoacid mono(hydrocarbyl) orthophosphate]; whereas ethylhexyl) orthophosphatc] bis [monoacid mono (2- those of generic Equation III are referred to as metal (III) ethylhexyl) orthophosphate]. [di(hydrocarbyl) orthophosphate] [mono(hy-drocarbyl) orthophosphate].
Broadly, the polyvalent metal halide employed in this in- This invention relates to the preparation of metal vention can be represented by the formula: organo orthophosphates. More particularly it relates to the preparation of such orthophosphates by reacting an R nMXn organic hydroxyl compound with a polyvalent metal halide and phosphorus pentcxide.
Metal organo orthophosphates can be prepared by reacting an organic acid orthophosphate with a polyvalent metal halide. The commercially available organic acid orthophosphates are generally mixtures of the monoand diacid orthophosphates in various proportions and free phosphoric acid is often present as an impurity. A metal organo orthophosphate of reproducible composition is difiicult to obtain from the commercially available organic acid orthophosphate reactants. Also, it is often necessary to remove the free phosphoric acid impurity prior to reaction with the polyvalent metal halide.
It has now been found that metal organo orthophosphates can be prepared by reacting an organic hydroxyl containing compound with a polyvalent metal halide and phosphorus pentoxide in an inert organic solvent. The reaction is conducted by simply admixing the reactants at a temperature of from about 10 C. to about 120 C. In the reaction, the halide groups of the metal are displaced to form a salt of the metal with at least two orthophosphate groups Whereas the monohydric organic compound 20 carbon atoms, (n) is an integer of 0 to 2, M is a polyvalent metal, X is a halogen and (n) is an integer of at least 2, such as 2 to 4 or 6 and the total of (n) and (ri') is equal to the valence of the metal M. Preferably the polyvalent metal halide is one represented by the formula MX wherein M is a polyvalent metal having a valence of 2-4, X is a halogen and n is an integer equal to the valence of the metal, i.e. 24. Illustratively the metal can be one from Group II, Group IV, Group VI and Group VIII of Mandeleeffs Periodic Arrangements of the Elements. A copy of this arrangement, referred to herein as the Periodic Arrangement, can be found on pages 3l2313 of the Handbook of Chemistry and Physics, 29th edition (1945). The preferred metals employed in this invention are the tetravalent metals of Group IV which have an automatic number of 22 to 40 such as titanium and zirconium. The halogen can be fluorine, chlorine, bromine or iodine and preferably chlorine.
Illustrative of specific polyvalent metal halides there can be mentioned: magnesium chloride; magnesium fluoride; calcium bromide, zine bromide; zinc chloride; barium co ple s 0 6 Or more Ester g p 011 each f the OfthO- chloride; mercuric chloride; stannous chloride; stannic phosphate groups attached to the metal. In addition to the chloride; lead chloride; titanium trichloride; titanium tetraester formation and linkage to the metal, one or more of chloride; titanium tetrafiuoride; titanium tetrabromide;
wherein R is a hydrocarbon group having from 1 to about.
titanium tetraiodide; germanium tetrachloride; molybdenum tetrachloride; chromic chloride; zirconium tetrachloride; zirconium tetrabromide; cobaltic chloride; cobaltous chloride; nickel bromide; nickel chloride; dibenzyl tin dibromide; dibenzyl tin dichloride; diethyl tin dibromide; disioamyl tin dichloride; diphenyl tin dibromide; ethyl propyl tin dichloride; ethyl tin triiodide; and the like.
The organic hydroxyl compound can have from 1 to about 30 carbon atoms. Preferably the organic hydroxyl compound is a monohydroxy hydrocarbon which can be represented by the formula ROH wherein R is a hydrocarbon group having from 1 to 30 carbon atoms and preferably from about 6 to about 22 carbon atoms. The hydroxyl group can be linked to an aliphatic, cycloaliphatic or aromatic hydrocarbon group. The monohydroxy, hydrocarbon can thus be alkanol, alkenol, cycloalkanol, cycloalkenol, phenol, phenalkanol, alkphenol and the like. Preferably the monohydroxy hydrocarbon is alkanol and particularly branched chain alkanol. Illustrative of specific monohydroxy hydrocarbon reactants there can be mentioned: methanol; ethanol; propanol; isopr-opanol; bu-
'tanol; isobutanol; 2-ethylhexanol; octanol; nonanol; 4.9-
dipropyldodecanol; 2,2,3-trirnethylheptanol; 3-ethylnonanol; 2-methyl-5-isopentylhendecanol; dodecanol; 6,7-dipentyldodecanol; 9,12-dimethyleicosanol; oleyl alcohol; linoleyl alcohol; 3-pentene-2-ol; cyclohexanol; 3-isopropylcyclohexanol; 4-decen-l-ol; 4-octylphenol; 4-isopropylphenol; 4 phenyl l-hydroxydodecane; phenol; alphanaphthol; benzyl alcohol; and the like. In the process of this invention either one or a mixture of organic hydroxyl compounds can be employed. Also, the hydrocarbon portion of the hydroxyl containing organic compound can be substituted with various groups which do not interfere with the reaction. Illustrative of substituent groups on the hydrocarbon group there can be mentioned nitro groups, such as in nitroalkanols, e.g. nitroethanol, and ammonium groups such as in ammonium alkenols, e.g. the lauric acid salt of ethanolamine.
The temperature employed in the process of this invention can vary over a wide range such as that of from about C. to about 120 C., preferably from about C. to about 110 C. and particularly from about C. to about 105 C.
The molar ratio of the reactants employed in the process of this invention can vary over a wide range such as that of from about 0.1 to 5 moles of phosphorus pentoxide and from about 1 to about 10 moles of the organic hydroxyl compound per mole of the metal halide and P eferably from about 0.5 to 3 moles of phosphorus pentoxide and 2 to 8 moles of the organic hydroxy compound per mole of the metal halide. The optimum molar ratio will, of course, vary with the particular reactants and particularly with the number of halogens attached to the metal, as can be seen from the hereinabove generic Equations I-III. It is preferred that the organic hydroxyl compound be added to a mixture of the metal halide and phosphorus pentoxide in an inert organic solvent at a temperature not higher than about 60 C. such as that of from about 10 C. to about 60 C. Addition of the organic hydroxyl compound to a mixture of phosphorus pentoxide and the metal halide is preferred since it minimizes reaction of the metal halide directly with the organic hydroxyl compound. Reaction of the metal halide and organic hydroxyl compound eliminates available reaction sites on the metal for the phosphate due to formation of a metal salt of the hydroxyl reactant. The initial contact of the hydroxyl reactant with the mixture of phosphorus pentoxide and metal halide is preferably at a temperature no higher, or below, 60 C. to prevent unduly rapid reaction rates. After the organic hydroxyl compound has been admixed with the phosphorus pentoxide and metal halide, the reaction is preferably completed by raising the reaction temperature, e.g. from about 80 C. to the maximum temperatures of the reaction hcreinbefore set forth, such as about 110 C. Also, it is desirable to provide means for removing the hydrogen halide formed in the reaction. In adding the organic hydroxyl compound to the mixture of phosphorus pentoxide and metal halide, a stoichiometric excess of the hydroxyl reactant can be employed in order to improve the yield of desired end product. However, a large excess such as that of more than 1.5 or twice the calculated molar ratio of hydroxyl compound for the particular reaction is preferably avoided since it may be desirable to later separate the excess hydroxyl compound from the reaction mixture in order to recover the desired reaction product.
The reaction time in the process of this invention is not critical. Thus it can vary from less than about half an hour to two or three days and preferably from about 2 or 3 hours to a day or two.
The metal organo orthophosphates can be recovered from the reaction mixture by conventional techniques such as fractional distillation, chromatographic absorption and the like. However, it is possible, although not generally desirable, to use the products without separation from the reaction mixture as additives to hydrocarbon fuels or mineral lubricating oils.
Suitable inert organic solvents for the process of this invention include various classes of compounds such as hydrocarbons, halogenated hydrocarbons and others. By the expression inert it is mean that the solvent is inert to the reactants and reaction products under the reaction conditions. Suitable solvents include benzene, toluene, uxylene, o-xylene, m-xylene, hexane, heptane, octane, cyclohexane, methylcyclohexane, chlorobenzene, carbon tetrachloride, ethyl ether, tetrahydrofurane, and the like. Preferred organic solvents are the normally liquid hydrocarbons such as the various aromatic, aliphatic and cycloaliphatic hydrocarbons.
In a preferred method for operating the invention the equipment used in the reaction should be immune to attack by gaseous hydrogen halide. The reaction vessel should be equipped with a heater, a mechanical stirrer, a pressure equalizing addition vessel, a reaction temperature indicator, and an inlet for compressed dry air to displace by-product hydrogen halide through a reflux condenser that does not permit entry of moisture from the outside. It is highly desirable to maintain a water-free atmosphere in the reactor. Two moles of phosphorus pentoxide is dispersed uniformly by means of mechanical agitation in a hydrocarbon solvent such as anhydrous n-heptane in the reaction vessel. One mole of tetravalent metal halide is added next with enough stirring to prevent agglomeration of the materials. Finally six moles of monohydroxy hydrocarbon, in the pressure equalizing addition vessel, is added at a rate to produce a steady evolution of gaseous hydrogen halide. It is preferred to keep the temperature of the reactants below about 60 C. during this step. When the addition is completed, the temperature of the reactants is raised from about C. to about 105 C. If evolution of by-product hydrogen halide begins to moderate, dry air is passed through the solution to hasten the displacement of the acid vapor in order to promote the reaction. As soon as the liberation of hydrogen halide is completed, the n-heptane and any unreacted hydroxyl compound are removed by distillation in vacuo. The residue in the vessel is the desired metal organo acid orthophosphate which can be obtained in to 99% yield based on metal halide used.
The metal organo orthophosphates prepared by the process of this invention have utility as additives in bydrocarbon fuel compositions, e.g. gasoline. When used in gasoline, small quantities of the metal organo orthophosphates, e.g. 100 parts per million based on the weight of the gasoline composition, impart rust inhibition, surface ignition suppression, carburetor detergency, carburetor icing alleviation, and reduction in octane requirement increase to the gasoline composition. Also, owing to their ability to reduce static friction the metal organo orthophosphates have utility as anti-wear agents in mineral oil lubricants wherein they can be employed in concentrations of about 1% by Weight of the composition. It is, however, desirable that the metal organo orthophosphates which have a free acid group, e.g. those of the hereinabove described generic Equations I and II, be neutralized with an organic amine prior to their use as hydrocarbon additives. Illustratively, the free acid groups can be neutralized at about 30 C. by contact with oleyl amine.
21320 TiCh 6 Illustrative of organo metal orthophosphates produced by the reaction of the hereinbefore described generic Equation I there can be mentioned: nickel (II) [di(2- ethylhexyl) orthophosphate] [monoacid mono(2-ethylhexyl) orthophosphate]; nickel (II) [di(4-octylphenyl) orthophosphate] [monoacid mono(4-octylphenyl) orthophosphate]; cobalt (II) [di(Z-ethylhexyl) orthophosphate] [monoacid mono(2-ethylhexyl) orthophosphate]; lead (II) [di(Z-ethylhexyl) orthophosphate] [monoacid mono(2-ethylhexyl) orthophosphate]; barium (II) [di(2- ethylhexyl) orthophosphate] [monoacid mono(2-ethylhexyl) orthophosphate]; calcium (II) [di(Z-ethylhexyl) orthophosphate] [monoacid mono(2-ethylhexyl) orthophosphate]; magnesium (II) [di(Z-ethylhexyl) orthophosphate] [monoacid mono(2-ethylhexyl) orthophosphate]; magnesium (II) [di(4-octylphenyl) orthophosphate] [monoacid mono(4-octylphenyl) orthophosphate]; and the like.
Illustrative of metal organo orthophosphates which can be prepared in accordance with the hereinbefore described generic Equation II, there can be mentioned: titanium (IV) bis[di(Z-ethylhexyl) orthophosphate] bis[monoacid mono (2-ethylhexyl) orthophosphate] titanium (IV) bis[di(4-octylphenyl) orthophosphate] bis[monoacid mono(4-octylphenyl) orthophosphate]; titanium (IV) bis[di(ethyl) orthophosphate] bis[monoacid mono(ethyl) orthophosphate]; titanium (IV) [di(ndodecyl) orthophosphate] bis[monoacid mono(n-dodecyl) orthophosphate]; titanium (IV) bis[di(oleyl) orthophosphate] bis[monoacid dioleyl orthophosphate]; titanium (IV) bis[dibenzyl orthophosphate] bis[monoacid monobenzyl orthophosphate]; zirconium (IV) bis[di(2 ethylhexyl) orthophosphate] bis[monoacid mono(2-ethylhexyl) orthophosphate]; zirconium (IV) bis[di(4 octylphenyl) orthophosphate] bis[monoacid mono(4-octylphenyl) orthophosphate]; zirconium (IV) bis[dioleyl orthophosphate] bis[monoacid (monoleyl) orthophosphate]; titanium (IV) bis[di(cyclohexyl) orthophosphate] bis[monoacid mono(cyclohexy) orthophosphate]; titanium (IV) bis[di(cresyl) orthophosphate] bis[monoacid mono(cresyl) orthophosphate]; titanium (IV) bis[di(eicosyl) orthophosphate] bis[monoacid mono(eicosyl) orthophosphate]; titanium (IV) bis[mono (isobutyl) mono(4 octylphenyl) orthophosphate] [monoacid mono (isobutyl) orthophosphate] [monoacid mono (4-octylphenyl) orthophosphate]; stannic (IV) bis[di(Z-ethylhexyl) orthophosphate] bis[monoacid mono(2-ethylhexyl) orthophosphate]; stannic (IV) bis[di(4-octylphenyl) orthosphosphate] bis[monoacid mono(4-octylphenyl) orthophosphate]; germanium (IV) bis[di(2 ethylhexyl) orthophosphate] bis[monoacid mono(Z-ethylhexyl) orthophosphate]; and the like. Illustrative of mental organo orthophosphates which can be prepared by the reaction shown in the hereinbefore generic Equation III with a trivalent metal there can be mentioned: titanium (III) [di(Z-ethylhexyl) orthophosphate]; [mono(Z-ethylhexyl) orthophosphate]; titanium (III) [di(4-octylphenyl) orthophosphate] [mono(4-octylphenyl) orthophosphate]; zirconium (III) [di(2-ethylhexyl) orthophosphate] [mono(2-ethylhexyl) orthophosphate]; cobaltic (III) [di(oleyl) orthophosphate] [mono (oleyl) orthophosphate]; and the like.
EXAMPLE 1 Titanium (IV) bis[di(Z-ethylhexyl) orthophosphate] bis[mono(2-ethylhexyl) monoacid orthophosphate] is obtained from the reaction of 2 moles of phosphorous pentoxide and one mole of titanium tetrachloride with 6 moles of 2-ethyl-1-hexanol as shown below:
\ /O O\ OR CHCHzOH (R02) 19 Ti P 4HCl 0 a O CH 2 wherein R is 2-ethy1hexyl.
To a suitable reaction vessel equipped with a mechanical stirrer, stoppered pressure equalizing addition funnel, thermometer, gas inlet tube, and a reflux condenser protected with a drying tube, there were added 400 ml. of anhydrous n-heptane and 71.0 g. (0.5 mole) or phosphorus pentoxide. With the stirrer going at a rate to insure a uniform dispersion 47.4 g. (0.25 mole) of titanium tetrachloride was added next. Finally 215 g. (1.65 moles) of 2-ethyl-1-hexanol, contained in the pressure equalizing addition funnel, was run into the reaction vessel at a rate such that the temperature of the reactants did not rise above 60 C. When this step was completed, the solution was homogeneous. The reactants were then heated at 98- 103 C., and when evolution of hydrogen chloride moderated, dry air was passed through the solution to displace the acid gas more rapidly and to accelerate the reaction. When further evolution of hydrogen chloride was no longer observed, as revealed by Congo red indicator, the n-heptane and any unreacted octanol were removed by distillation in vacuo. The final temperature of the residual product in the reaction vessel was 175 at 25 mm. A very pale yellow syrupy product was obtained weighing 275.0 g., which is 99% of theory based on the metal halide. Inspection data were as follows Calculated formula weight for TiC H P O 1109.15
Calculated, percent:
Titanium 4.32
Phosphorous 11.17 Found, percent:
Titanium 4.37; 4.30
Phosphorus 11.24; 11.15 Refractive index, n 1.4750 Density, d 1.0836 Viscosity, SUS
210 F. 665.5 ASTM color /2 EXAMPLE 2 In the manner described in Example 1 a mixture of two moles (284 g.) of P 0 and one mole (233 g.) of zirconium tetrachloride in anhydrous n-heptane is reacted with a blend of 3.1 moles (96 g.) of methanol and 3.1 moles (404 g.) of 2-ethylhexanol to produce zirconium (IV) bis[mono (methyl) mono(2ethylhexyl) orthophosphate] [monoacid mono (2-ethylhexyl) orthophosphate] [monoacid mono(methyl) orthophosphate] EXAMPLE 3 In the manner described in Example 1,142 g. (1 mole) of P 0; and g. (1 mole) of anhydrous nickel chloride are dispersed uniformly in 1500 ml. of dry octane. Four hundred and thirty grams (3.3 moles) of 2,2,4-trimethyl- 1-pentanol is added. The reaction mixture is heated at 105 C. until evolution of I-ICl stops. The solvent is removed by distillation in vacuo, the final temperature being at 25 mm. pressure. The product is, nickel (II) [di(2,2,4- trirnethyl-l-pentyl) orthophosphate]; [monoacid mono(2, 2,4-trimethyl-1-pentyl) orthophosphate].
7 EXAMPLE 4 Phosphorus pentoxide 71.0 g. (0.5 mole) and 65.1 g. (0.25 mole) of stannic chloride are dispersed in 500 ml. of toluene, A blend, consisting of 103 g. (0.5 mole) of octyl phenol and 74.1 g. (1 mole) of iso-butano-l, is added to the toluene dispersion in the manner described in Example 1. When evolution of hydrogen chloride is completed upon heating the reaction solution at 100 C., the solvent is removed by distillation at reduced pressure. The product can be represented by the following formula:
To a well stirred and dispersed mixture of 14.2 g. (0.1 mole) of P and 37.2 g. (0.1 mole) of dibenzyltin dichloride in 200 ml. of anhydrous n-heptane, there is added 18 g. (0.3 mole) of anhydrous isopropanol. When no more HCl is liberated at 98 C. the solvent is removed by distillation at reduced pressure, the final temperature being 150 C. The product is dibenzyltin bis [monoacid mono(isopropyl) orthophosphate] of the formula:
0 /o Cal-I7 EXAMPLE 6 Following the procedure of Example 1, the corresponding phenyl, benzyl, and cyclohexyl metal organo orthophosphates can be prepared by simply substituting the stoichiometric equivalent quantity of phenol, benzyl alcohol and cyclohexanol respectively for the 2-ethylhexanol employed in Example 1.
What is claimed is:
1. A process for preparing a metal organo orthophosphate which comprises: (a) contacting, in an inert organic solvent, phosphorus pentoxide; and (b) a polyvalent metal halide of the formula MX wherein M is a polyvalent metal, selected from the group consisting of magnesium, calcium, zinc, barium, mercury, lead, titanium, germanium, molybdenum, chromium, zirconium, cobalt, nickel and tin, X is a halogen and .n is equal to the valence of the metal M; with (c) a monohydroxy hydrocarbon having from 1 to about carbon atoms at a tempera ture of from about 10 C, to about 120 C.
2. A process of claim 1 wherein the monohydroxy hydrocarbon is alkanol having from about 6 to about 22 carbon atoms and is added at a rate to produce a steady evolution of gaseous hydrogen halide.
3. A process of claim 1 wherein the metal is tetravalent titanium.
4. A process for preparing a metal organo orthophosphate which comprises: (a) contacting, at a temperature 3 of from about 20 C. to about C., a monohydroxy hydrocarbon having from 1 to about 30 carbon atoms; with (b) a mixture of titanium tetrachloride and phosphorus pentoxide in an inert organic solvent.
5. The process of claim 4 wherein from about 0.5 to about 3 moles of phosphorus pentoxide and from about. 2 to about 8 moles of monohydroxy hydrocarbon are contacted with each mole of titanium tetrachloride.
6. The process of claim 5 wherein the monohydroxy hydrocarbon is alkanol.
7. The process of claim 5 wherein the monohydroxy hydrocarbon is phenylalkanol.
8. A process for preparing a metal organo orthophosphate which comprises: (a) contacting, at a temperature of from about 20 C. to about 110 (3., a monohydroxy hydrocarbon having from 1 to about 30 carbon atoms; with (b) a mixture of zirconium tetrachloride and phosphorus pentoxide in an inert organic solvent,
9. A process of claim 8 wherein the monohydroxy hydrocarbon is alkanol.
10. A process for preparing a metal organo orthophosphate of the formula:
wherein M is a tetravalent metal, each R is hydrocarbyl of from 1 to about 30 carbon atoms, which comprises: (a) reacting at a temperature of from about 20 C. to about 110 C., a monohydroxy hydrocarbon having from 1 to about 30 carbon atoms; with (b) a mixture of tetravalent metal halide of the formula MX wherein M is tetravalent metal and X is halogen and phosphorus pentoxide in an inert organic solvent.
11. A process of claim 10 wherein M is a metal having an atomic number of 22 to 40 from Group IV of the Periodic Arrangement and about 2 moles of phosphorus pentoxide and about 6 moles of the monohydroxy hydrocarbon are reacted with each mole of the tetravalent halide.
12. A process of claim 11 wherein M is titanium.
13. A process for preparing a metal organo orthophosphate of the formula:
wherein each R is hydrocarbyl of from 1 to about 30 carbon atoms and M is a divalent metal which comprises: (a) contacting at a temperature of from about 20 C. to about 110 C. a monohydroxy hydrocarbon having from 1 to about 30 carbon atoms; with a mixture of a divalent metal halide of the formula MX wherein M is a metal and X is halogen and phosphorus pentoxide in an inert organic solvent.
14. A process for preparing a metal organo orthorphosphate of the formula:
wherein R is hydrocarbyl of from 1 to about 30 carbon atoms and M is a trivalent metal which comprises: (a) contacting, at a temperature of from about 20 C. to about 110 C. a monohydric hydrocarbon having from 1 to about 30 carbon atoms; (b) with a mixture of a metal halide of the formula MX wherein M is a trivalent metal and X is halogen and phosphorus pentoxide in an inert organic solvent.
15. A process for preparing titanium (IV) -bis[di(2- ethylhexyl) orthorphosphate] .bis[n1onoacid mono(2- ethylhexyl) orthophosphate]; which comprises: (a) dispersing phosphorus pentoxide and titanium tetrachloride in an inert hydrocarbon solvent; (b) adding and reacting References Cited UNITED STATES PATENTS 2,272,668 2/1942 Honel 260933X 10 Farrington et a1. 2604297 X Mack et a1. 260439X Fortress et a1. 260980 Otto et a1. 260933X Giammaria 260933 X Heyden 2'60429.5 X Wurstner 260429.7X Revukas 260--429.5 X
10 TOBIAS E. LEVOW, Primary Examiner.
H. M. S. SNEED, Assistant Examiner.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US350113A US3401184A (en) | 1964-03-06 | 1964-03-06 | Metal organo phosphate preparation process |
US659246A US3491133A (en) | 1964-03-06 | 1967-05-23 | Metal organo phosphates and amine salts thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US350113A US3401184A (en) | 1964-03-06 | 1964-03-06 | Metal organo phosphate preparation process |
Publications (1)
Publication Number | Publication Date |
---|---|
US3401184A true US3401184A (en) | 1968-09-10 |
Family
ID=23375295
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US350113A Expired - Lifetime US3401184A (en) | 1964-03-06 | 1964-03-06 | Metal organo phosphate preparation process |
Country Status (1)
Country | Link |
---|---|
US (1) | US3401184A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4233253A (en) * | 1978-12-26 | 1980-11-11 | Standard Oil Company (Indiana) | Method for the preparation of metal salts of phosphorus acid esters |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2272668A (en) * | 1939-02-10 | 1942-02-10 | Reichhold Chemicals Inc | Partial phosphoric esters and process for preparing same |
US2329707A (en) * | 1941-01-13 | 1943-09-21 | Standard Oil Co California | Metal organophosphates and method of preparing the same |
US2409774A (en) * | 1942-10-08 | 1946-10-22 | Advance Solvents & Chemical Co | Drier metal salt and process of making it |
US2676975A (en) * | 1950-08-31 | 1954-04-27 | Celanese Corp | Process for production of phosphate esters |
US2790767A (en) * | 1956-10-30 | 1957-04-30 | Socony Mobil Oil Co Inc | Grease compositions containing complex alkaline earth metal salts |
US2790765A (en) * | 1955-10-20 | 1957-04-30 | Socony Mobil Oil Co Inc | Mixed metal complex salts of phosphoric acid esters and mineral oil compositions containing the same |
US2885417A (en) * | 1955-11-10 | 1959-05-05 | Bohme Fettchemie Gmbh | Organic complex salts of polyvalent metals and methods of producing the same |
US3215715A (en) * | 1961-09-22 | 1965-11-02 | Lubrizol Corp | Metal-containing phosphate complexes and method of preparing same |
US3275668A (en) * | 1961-07-31 | 1966-09-27 | Cities Service Oil Co | Organometallic orthophosphates |
-
1964
- 1964-03-06 US US350113A patent/US3401184A/en not_active Expired - Lifetime
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2272668A (en) * | 1939-02-10 | 1942-02-10 | Reichhold Chemicals Inc | Partial phosphoric esters and process for preparing same |
US2329707A (en) * | 1941-01-13 | 1943-09-21 | Standard Oil Co California | Metal organophosphates and method of preparing the same |
US2409774A (en) * | 1942-10-08 | 1946-10-22 | Advance Solvents & Chemical Co | Drier metal salt and process of making it |
US2676975A (en) * | 1950-08-31 | 1954-04-27 | Celanese Corp | Process for production of phosphate esters |
US2790765A (en) * | 1955-10-20 | 1957-04-30 | Socony Mobil Oil Co Inc | Mixed metal complex salts of phosphoric acid esters and mineral oil compositions containing the same |
US2885417A (en) * | 1955-11-10 | 1959-05-05 | Bohme Fettchemie Gmbh | Organic complex salts of polyvalent metals and methods of producing the same |
US2790767A (en) * | 1956-10-30 | 1957-04-30 | Socony Mobil Oil Co Inc | Grease compositions containing complex alkaline earth metal salts |
US3275668A (en) * | 1961-07-31 | 1966-09-27 | Cities Service Oil Co | Organometallic orthophosphates |
US3215715A (en) * | 1961-09-22 | 1965-11-02 | Lubrizol Corp | Metal-containing phosphate complexes and method of preparing same |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4233253A (en) * | 1978-12-26 | 1980-11-11 | Standard Oil Company (Indiana) | Method for the preparation of metal salts of phosphorus acid esters |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US3267149A (en) | 4-hydroxybutyl phosphorus compounds | |
US2500022A (en) | Dialkyl alkoxy methane phosphonates and method of preparation | |
US3338935A (en) | Amine salts of metal organo orthophosphates | |
US3401184A (en) | Metal organo phosphate preparation process | |
US3491133A (en) | Metal organo phosphates and amine salts thereof | |
US2903487A (en) | Metallic derivatives of hindered phenols | |
US2678940A (en) | Preparation of aliphatic triesters of phosphorous acid | |
US3291865A (en) | Cyclic polymeric phosphonitrilate compositions | |
US3354189A (en) | Metal (hydrocarbyl and acid hydrocarbyl pyrophosphates) and amine adducts | |
US3412118A (en) | Salts of 2, 6-and 2, 4, 6-substituted primary aryl phosphites | |
US3334978A (en) | Hydrocarbon fuel composition | |
US3271481A (en) | 2, 6-disubstituted primary aryl phosphites and phosphorodihalidites and processes for the manufacture thereof | |
CA1139311A (en) | Preparation of trimethyltin chloride from dimethyltin dichloride (improved method) | |
US2728789A (en) | Acetylenic tertiary phosphite esters | |
US4118435A (en) | Catalyzed production of phosphorous and phosphonous acid ester chlorides | |
US2709174A (en) | Method of preparing esters of titanic acid | |
US2984680A (en) | Method for preparing diphenyl phosphites | |
US2948599A (en) | Gasoline fuel compositions | |
EP0308264A2 (en) | Lubricant additive comprising mixed non-aryl diol/phosphorodithioate-derived borates | |
US3347890A (en) | Triorganotin carbodhmides and isoureas and the preparation thereof | |
US3470270A (en) | Production of phosphorus acid esters | |
US3491024A (en) | 2,6-disubstituted primary aryl phosphites,their salts and phosphorodihalidites and processes for the manufacture thereof | |
US3088814A (en) | Organo-bimetallic compositions | |
US3329742A (en) | Lubricating oils containing phosphorus products | |
US2223329A (en) | Organic phosphates |